Gas-phase reactions of HONO with HNO and NH3: an ab initio MO/TST study
- 化学化工－已发表论文 
The reduction of MONO by HNO and NH3 has been investigated by means, of ab initio molecular orbital and transition-state theory (TST) calculations. The main reaction channels for the HNO + trans-MONO (cis-HONO) reactions are those proceeding via five-member ring transition states, leading to the production of NO and H2O. In the temperature range 300-1000 K, TST calculations predict an A factor of 2.25 x 10(10) cm(3) mol(-1) s(-1) (or 3.63 x 10(10) cm(3) mol(-1) s(-1)) and an apparent activation energy of 20.9 kcal/mol (or 21.9 kcal/mol) for the HNO + trans-HONO (or cis-HONO) reaction. In the NH3 + HONO system, the reaction NH3 + cis/trans-HONO --> H2NNO + H2O with barrier heights centering around 34 kcal/mol can occur at high temperatures. The reversible H-atom exchange reaction NH3 + cis-HONO double left right arrow H2NH-O(H)NO double left right arrow NH2H + cis-HONO occurs readily. The calculated rate constant for the reaction at 300 K is 1.06 x 10(6) cm(3) mol(-1) s(-1), in reasonable agreement with the experimental value of 2.2 x 10(6) cm(3) mol(-1) s(-1).